CN115253706B - Preparation method and application for preparing ultra-long tubular membrane through water bonding - Google Patents
Preparation method and application for preparing ultra-long tubular membrane through water bonding Download PDFInfo
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- CN115253706B CN115253706B CN202210924758.9A CN202210924758A CN115253706B CN 115253706 B CN115253706 B CN 115253706B CN 202210924758 A CN202210924758 A CN 202210924758A CN 115253706 B CN115253706 B CN 115253706B
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- -1 specifically Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
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- 230000003068 static effect Effects 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
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- 238000005530 etching Methods 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000012527 feed solution Substances 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 229940097068 glyphosate Drugs 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/243—Dialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing an ultra-long tubular membrane by water bonding, and the ultra-long tubular membrane is arranged in a 3D printing dialysis tank for diffusion dialysis to separate acid-containing or alkali-containing feed liquid, specifically, coating liquid is firstly prepared, a flat sheet is formed after coating and volatilizing, then a plurality of rectangular strips with short and long dimensions are cut into pieces, the long rectangular strips are rolled on a cylindrical support, water is coated on one side of each rectangular strip to restore the viscosity, a tube is formed after the other side is bonded, and the plurality of tubes are connected through the short rectangular strips, and the ultra-long tubular membrane is obtained after heat treatment; the ultra-long tubular membrane is arranged in a 3D printing dialysis tank with four porous cylinders, is applied to separating acid-containing or alkali-containing feed liquid in the diffusion dialysis process, has the characteristics of large surface area, high tensile strength and no liquid leakage, and has the advantages of light weight, high filling density and large treatment capacity.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a preparation method and application for preparing an ultra-long tubular membrane by water bonding.
Background
Diffusion dialysis is a membrane process that uses the difference in concentration across the membrane as the driving force to separate the feed solution. Initially, one side of the membrane is high-concentration feed liquid, and the other side is water. Driven by concentration differences, active components in the feed solution, e.g. H + Or OH (OH) - The ions can selectively penetrate through the membrane to enter one side of water, and after a period of time, active components in the feed liquid side are separated to form residual liquid; and the active components are recovered from the water side to obtain a recovery liquid. According to the principle of diffusion dialysis, the structural design of the membrane material is a key for improving the separation performance, the currently used polymer membrane is generally in a flat plate shape, and the main direction of research is to improve the chemical structure and components of the membrane and optimize the separation capability of the membrane. During separation, the flat membrane is placed in a conventional static diffusion dialyzer or dynamic diffusion dialyzer, and is fixed by various fittings such as a baffle plate, a gasket, a screen, a nut, etc., and is shaped on both sides of the membraneTwo flow channels of feed liquid and water are formed, and the purpose of separation is achieved. For example, commercial cathode films DF-120, TWDD series flat-plate films produced by Shandong Tianwei corporation all go to practical use by being installed in a plate-and-frame diffusion dialyzer.
Chinese patent ZL201210206572.6 discloses a method for preparing a flat cathode film by using brominated polyphenylene oxide (BPPO) and polyvinyl alcohol (PVA), wherein the flat cathode film can be applied to separating HCl/FeCl in static diffusion dialysis process 2 The solution, the membrane has high acid transferring speed and high selectivity. However, since the flat membrane is assembled in the static diffusion dialyzer, which comprises fittings such as an organic glass tank, a gasket, a nut, a stirrer and the like in addition to the membrane, the weight is high, the cost is high, the effective area of the membrane is limited, the weight ratio of the membrane in the static diffusion dialyzer is only 0.042% (the static diffusion dialyzer with the weight of 1.28kg only contains one flat membrane with the weight of 0.54 g), and the speed of treating the feed liquid is very slow.
Chinese patent ZL201710256743.9 discloses a method for preparing a non-charged flat membrane by using PVA and alkoxy silane, which is applied to a dynamic diffusion dialysis process, wherein the membrane has lower hydrophilicity, a plurality of flat membranes are assembled into a dynamic diffuser, HCl components in glyphosate acidification liquid can be effectively separated, and water permeation is lower in the dynamic diffusion dialysis process. The dynamic diffusion dialyzer, however, comprises, in addition to the membrane, two massive plexiglas plates, washers, screens, nuts and the like, which represent a major cost and weight. The weight ratio of 7 membranes in the dynamic diffusion dialyzer was also only 0.6%, and the rate of the treatment stock solution was still insufficient.
The method comprises loading TWDDA type negative film produced by Shandong Tianwei film company into dynamic diffusion dialyzer, and removing F from feed liquid containing metal ion - And Cl - Ions. The commercial membranes used in the report were uniform and flat in structure and the membranes could only be fitted into a conventional diffusion dialyzer. Although the components of the recovery liquid can be adjusted by changing the flow rates of the feed liquid and the water, the flux and the selectivity during separation cannot be fundamentally changed due to the single membrane structure.
Separating and purifying (Separation andPurificationTechnology,235,2020,116147) by using concentrated viscous glue, namely 15wt% polyvinyl alcohol solution as an adhesive, bonding two sides of a flat plate membrane to prepare a tubular membrane with the length of 30-60 cm, wherein the membrane has proper hydrophilicity, and can separate HCl-containing glyphosate acidification liquid in the diffusion dialysis process. However, the glue-bonded tubular film has four defects in the preparation and application processes, (1) the glue has high viscosity, is difficult to uniformly coat on the film, has low coating speed and large dosage, so that the adhesive layer is uneven and is easy to wrinkle, and the thickness of the adhesive layer is increased. During bonding, the two side edges of the flat plate film are bonded together in a face-to-face mode, so that the bonding layer cannot contact with the solution in the pipe in the diffusion dialysis process, and the separation capability is lost. More seriously, due to uneven and 'face-to-face' bonding of the bonding layer, the mechanical properties of the bonded parts are insufficient, and when the pressure is high or the bonding parts are used for a period of time, liquid leakage phenomenon occurs at the bonded parts, so that the whole tubular film fails. (2) The tubular membrane has short length, and the length is limited to 30-60 cm due to the lack of a connecting method, so that the membrane area is insufficient, and the tubular membrane is difficult to apply to the field of actual separation. (3) After the liquid is filled in the tubular membrane, the tubular membrane can be in a V shape when the bending degree is too large, so that the flow of the liquid in the tubular membrane is blocked; (4) Tubular membranes lack a suitable dialyzer and can only be randomly and randomly bent to perform diffusion dialysis in a common plastic box, so that the membrane has insufficient packing density and small separation capacity per unit volume. When the density of the liquid in the tube is small, the tube membrane floats on the liquid in the plastic box, namely the liquid level of the mother liquid, so that the separation capacity is reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing an ultra-long tubular membrane by water bonding and a design method of a 3D printing dialysis tank required by the ultra-long tubular membrane. The ultra-long tubular membrane has a compact and nonporous structure, is long in macroscopic physical shape, can replace a traditional flat membrane, is arranged in a 3D printing dialysis tank and is applied to a diffusion dialysis process, and acid-containing or alkali-containing feed liquid is separated.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for preparing an ultra-long tubular film by water bonding, comprising the steps of:
s1, dissolving polyvinyl alcohol in water to form a polyvinyl alcohol solution with the mass concentration of 5-7%; the polyvinyl alcohol solution can be directly used as coating liquid, or the temperature of the polyvinyl alcohol solution is kept at 50-70 ℃, the component A is dropwise added into the polyvinyl alcohol solution according to the mass ratio of the component A to the polyvinyl alcohol of 0.05-0.5:1, after the dropwise addition is completed for 0.5-1.5 hours, the mixture is continuously stirred for 6-24 hours under heat preservation, so as to obtain the coating liquid, and the preparation of the coating liquid is completed;
s2, uniformly coating the coating liquid obtained in the step S1 on a glass plate, drying in a ventilation environment to obtain a uniform flat sheet, cutting the obtained flat sheet into rectangular strips with long and short dimensions, rolling the rectangular strips with long dimensions on a polytetrafluoroethylene tube to form a long tube shape, wherein the width of an overlapping area of a long tubular inner layer and an outer layer is 1-1.5 cm, coating water on the surface of the outer layer of the overlapping area to wet the surface of the overlapping area, bonding the two layers of overlapping areas by pressing the outer layer to form a single tube, and repeatedly preparing a plurality of single tubes;
s3, taking the two single tubes obtained in the step S2, wherein one end of each single tube is sleeved on the same polytetrafluoroethylene tube, so that the two ends are aligned and close; completely wrapping two ends of the rectangular strip with short dimensions to form an inner layer at the two ends and an outer layer of the rectangular strip, coating water on the outer layer to moisten the surfaces of the rectangular strip, bonding the two layers by pressing the rectangular strip to attach the inner layer, and connecting the two single tubes together through the rectangular strip to form a longer tube; repeating the steps, connecting a plurality of single pipes to form an ultra-long pipe, carrying out heat treatment on the ultra-long pipe, and preserving heat for 2-6 hours at 120-130 ℃ to obtain the ultra-long pipe type membrane.
Preferably, component A in step S1 is Tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), aminopropyl triethoxysilane (A1100), an aminated polyphenylene oxide hybrid solution (BPPO (+)/SiO) 2 ) Hydrogen-type sulfonated polyphenylene oxide hybrid solution (SPPO-H/SiO) 2 ) Or polysilicone copolymers.
Preferably, in the step S2, the length of the long rectangular strip is 30-90 cm, and the width is 5-9 cm; the length of the short rectangular strip is 5.5-9.5 cm, and the width is 3-5 cm.
Preferably, the amount of the water applied in the steps S2 and S3 is controlled to be 15 to 25cm per coating area 2 1mL of water is consumed, and the temperature of the water is controlled between 15 and 65 ℃.
Preferably, in step S3, the ultra-long tube includes 3 to 8 single tubes connected to each other.
The invention also discloses a design method of the 3D printing dialysis pool, which is used for installing an ultralong tubular membrane for diffusion dialysis and comprises the following steps:
the size and the model of the dialysis tank are designed through Rhino 7 and Shapr3D software, the 3D printing dialysis tank comprises a cuboid dialysis tank main body and four hollow porous cylinders, the dialysis tank main body comprises an inlet and an outlet, the porous cylinders are movably arranged at the bottom, and the porous cylinders can fix an ultralong tubular membrane in the dialysis tank for diffusion dialysis separation of acid-containing or alkali-containing feed liquid.
Preferably, the dialysis cell body has a volume of 4-10L, the porous cylinder has a diameter of 4-8 cm and a height of 10-18 cm.
Preferably, the method for fixing the ultra-long tubular membrane in the dialysis tank is that the ultra-long tubular membrane is coiled and hung outside a porous cylinder, then the porous cylinder is arranged at the bottom of the dialysis tank, feed liquid or water is introduced into the tubular membrane, corresponding water or feed liquid is introduced into the dialysis tank through an inlet as mother liquid, and the ultra-long tubular membrane is immersed in the mother liquid; after the treatment is completed, collecting the liquid and mother liquor in the ultra-long tubular membrane to obtain residual liquid and recovery liquid.
Preferably, the diffusion dialysis comprises three forms, static, semi-dynamic or dynamic;
when static diffusion dialysis is adopted, liquid is not input and output from two ports of the ultra-long tubular membrane, and neither the liquid in the tube nor mother liquid in the dialysis cell flows;
when semi-dynamic diffusion dialysis is adopted, one port of the ultra-long tubular membrane is used for inputting liquid, the other port is used for outputting liquid, and mother liquor in the dialysis tank does not flow;
in the case of dynamic diffusion dialysis, one port of the ultra-long tubular membrane is fed with liquid and the other port is fed with liquid. Mother liquor in the dialysis cell flows in from the inlet and flows out from the outlet.
Compared with the prior art, as shown in fig. 1, the invention has the beneficial effects that:
1. the invention uses water to coat one side of the flat membrane to restore the adhesiveness of the membrane surface, and then the other side is adhered to form a tube shape. Because the viscosity of water is small, the coating can be uniformly applied, the coating speed is high, the thickness of the film layer is not increased, the uniformity of the adhesive layer can be ensured, and the leakage phenomenon is avoided. The existing two-layer film compounding technology adopts methods of hot pressing, film coating liquid-glue adhesion, spraying and the like, and has the defects of complex operation, increased thickness, low speed, difficult uniformity and untight adhesion.
2. The invention uses polytetrafluoroethylene tube as support, and the flat film strip is curled on the tube to form a tube shape, and then two sides of the strip are adhered. The bonding mode enables the two sides of the strip film to be bonded in a face-to-back mode, and the thickness of the bonding layer is nearly doubled, but the bonding layer can still contact the solution inside the tube and the solution outside the tube in the diffusion dialysis process, so that the separation effect is achieved. More importantly, the fitting mode can greatly enhance the stretching resistance of the tubular film and prevent the rupture of the bonding layer. The reported tubular membranes do not use a support body in the lamination process, and can only produce lamination of face-to-face type, and the lamination layer has no separation capability in the diffusion dialysis process and can produce a cracking phenomenon under the action of pressure or corrosion.
3. The invention adopts the water bonding method, so that a plurality of pipes can be connected to form the ultra-long pipe type membrane, and the membrane area can meet the actual application requirement. Whereas the reported flat membrane requires multiple sheets in parallel to achieve the desired area, the parallel connection of multiple sheets requires the use of thick plates, washers, spacers, nuts, etc.
4. According to the invention, a 3D printing dialysis tank is designed aiming at the installation requirement of the ultra-long tubular membrane, the V-shaped bending phenomenon of the tubular membrane is overcome, the filling density of the tubular membrane is improved, and static, dynamic and semi-dynamic diffusion dialysis can be conveniently carried out. Although 3D printing membrane separation apparatuses have been studied in other fields of application, no relevant report has been made in the field of diffusion dialysis.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is a graph comparing the ultralong tubular membranes of the present invention with those reported in the literature (Sep. Purif. Technology. 235,2020, 116147);
FIG. 2 is a flow chart of the process of the present invention for water bonding to produce an ultralong tubular membrane and assembly into a 3D print dialyzer;
FIG. 3 is a schematic diagram of the dimensional structure of a 3D printing dialysis cell designed using Rhino 7 and shape 3D software in accordance with the present invention;
fig. 4 is an SEM image and a digital photograph of the adhesive layer and the tie layer of the ultralong tubular film of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1: preparation of 2m long PVA tubular film by Water bonding acid liquor was separated in a 3D printing dialysis tank
(1) Preparation of a coating liquid: PVA solid was dissolved in 95℃water to form a PVA solution having a mass concentration of 5% by weight.
(2) Preparation of a single tube: the 500ml va solution was coated on a 35 x 75cm large glass plate, and allowed to evaporate freely in a ventilated atmosphere to give a uniform flat sheet, which was peeled off from the glass plate, cut into 4 rectangular strips of 50 x 6.5cm in size, and 3 rectangular short strips of 7 x 4cm in size. A rectangular strip of 50X 6.5cm was taken and rolled onto a polytetrafluoroethylene tube of 1.6cm in outside diameter to form a long tube shape with an overlap region of 1.3cm in width between the inner and outer layers. Applying water to the outer surface of the overlapping region to wet the surface, thereby generating tackiness, and controlling the water amount to be 20cm per application area 2 1mL of water was consumed, and the outer layer was immediately pressed against the inner layer to bond the two overlapping areas, forming a single tube 50cm in length. By the same methodThree single tubes 50cm in length were prepared.
(3) Preparation of an ultralong tubular film: and (3) taking the two single pipes obtained in the step (2), and sleeving one end of each single pipe on the same polytetrafluoroethylene pipe, so that the two ends of the two single pipes are aligned and abutted. And the two ends of the single tube are completely wrapped by rectangular short strips with the size of 7 multiplied by 4cm to form a double-layer structure, wherein the inner layer is two ends of the single tube, and the outer layer is the rectangular short strips. Coating water on the outer layer to moisten the surface, wherein the water amount is controlled to be 20cm per coating area 2 1mL of water was consumed, and the two layers were bonded by pressing the rectangular strips against the inner layer, so that the two single tubes were connected together by the rectangular short strips to form a tube of 100cm in length. Repeating the steps, connecting another 2 single pipes on a pipe with the length of 100cm continuously to form an ultra-long pipe with the length of 200cm, taking the ultra-long pipe out of the polytetrafluoroethylene pipe, placing the ultra-long pipe into an oven, heating the temperature from 60 ℃ to 130 ℃ within 1h, and preserving the temperature at 130 ℃ for 4h to obtain the ultra-long pipe type membrane with the length of 200cm (namely 2 m). The ultra-long tubular membrane is soaked in water for storage, and with the help of the binding belt, two ends are connected with plastic pipes, and the effective length is changed to 195cm.
(4) Dialysis cell size and model were designed by Rhino 7 and shape 3D: as shown in FIG. 2, the dialysis cell comprises a cuboid main body and four porous cylinders, the size of the dialysis cell main body is 200 multiplied by 250 multiplied by 150mm, the dialysis cell comprises an inlet and an outlet, eight clamping grooves are formed in the bottom, and the clamping grooves can movably fix the four hollow porous cylinders. The diameter of the porous cylinder is 60mm, namely 6cm, and the height is 128mm, namely 12.8cm.
(5) Separating the acid by diffusion dialysis: with the aid of the tie, the ultra-long tubular membrane is wound and suspended outside the porous cylinder, which is then mounted at the bottom of the dialysis cell. Will be 0.5L H 2 SO 4 /FeSO 4 Introducing acid liquor into the tubular membrane, and introducing H into the acid liquor + Ion concentration of 3.1mol L -1 (M)、Fe 2+ The ion concentration was 0.26M. And 4L of water is injected into the dialysis pool through the inlet as mother liquor, and the ultra-long tubular membrane is immersed in the mother liquor and runs for 6 hours. When static diffusion dialysis is adopted, no liquid is input or output from two ends of the ultra-long tubular membrane, neither the liquid in the tube nor the mother liquid in the dialysis tank flows, and mother liquid is collected every 1h to obtainRecovering the liquid; when semi-dynamic diffusion dialysis is adopted, the speed of acid liquid input into one port of the ultra-long tubular membrane is 96, 150 or 196+/-1 mL h -1 The other port outputs residual liquid, the residual liquid is collected every 1h, and the mother liquid does not flow.
The tubular membranes were tested for various physical dimensions, as well as water content and coefficient of linear expansion, and methods of testing for water content and coefficient of linear expansion reference (Separation and PurificationTechnology,184,2017,1-11), digital photographs were taken of the adhesive layer of the tubular membrane, and the two single tube tie layers, and a cross-section test Scanning Electron Microscope (SEM) was taken. At the same time, sampling is carried out to test the corrosion resistance, namely, the sample is soaked in H at 40 DEG C 2 SO 4 /FeSO 4 And (5) placing the mixture in acid liquor for 4 days.
The test results show that the water content of the ultra-long tubular membrane is 95.7%, the linear expansion coefficient is 18%, the wet thickness of the non-bonding area is 0.10-0.12mm, the thickness of the bonding area is 0.20-0.23mm, the inner diameter of the cross section of the tube is 1.65cm, and the effective surface area is 980cm 2 The volume of the tube is 500+/-8 mL, which is far higher than the surface area and volume (122-324 cm) 2 40-75 mL); the weight percentage of wet membranes in the dialysis cell was 3.6%, which is much higher than the weight percentage of traditional flat membranes in the diffusion dialyzer (0.4-1.7%) (ref Separation and Purification Technology,235,2020,116147).
The digital photograph and SEM are shown in FIG. 4, and include (a) a section of the adhesive layer before etching, (b) a section of the adhesive layer after etching, (c) a surface of the adhesive layer after etching, and (d) a surface of the connecting layer of two pipes after etching, the film etching environment being H at 40 ℃C 2 SO 4 /FeSO 4 (1.5+0.26M) solution for 4 days; SEM pictures show that the two layers of water bonded cross-section are flat and uniform without obvious voids, and after corrosion, the cross-section remains compact, indicating that the two layers of water bonded have been fully bonded together, and microscopically without an interfacial layer. The digital photo shows that the surface of the corroded bonding layer still keeps compact, and the phenomenon of falling off and layering is avoided, so that the bonding layer is also applicable to two single-tube connecting layers. Thus, the water bonding shows the effect of adhesion and corrosion resistance.
Static diffusionAfter 4H of separation, H + The recovery rate of ions reaches 70.7 percent, fe 2+ The rejection rate of ions is 87.9%; after 6H, H + The recovery rate of (C) was 80.7%, fe 2+ The rejection rate of ions was 80%. In the semi-dynamic diffusion dialysis process, H in residual liquid flowing out of the tube is prolonged along with time + The ion concentration is firstly reduced rapidly and then stabilized gradually, and Fe 2+ The ion concentration drops slowly. As the flow rate increases, the acid concentration in the raffinate becomes greater. When the flow rate is 96mL h -1 At the time of 6 hours, H in the residual liquid + The ion concentration is 0.89M, the recovery rate is up to 91.2%, and the retention rate is 86.1%; when the flow rate is 196mL h -1 At the time of 6 hours, H in the residual liquid + The ion concentration was 1.65M, the recovery rate was 50.0%, and the rejection rate was 95.4%.
To compare the effect of the adhesive "face-to-face" bonding (Separation and Purification Technology,235,2020,116147) reported in the literature to the "face-to-back" bonding with the water of the present invention, we prepared tubular films in the literature bonding manner and tested the mechanical properties of the inventive ultralong tubular films, and tested the tensile test of the samples using an SC-1000 tensile tester manufactured by Shenzhen intelligent limited. Intercepting an annular sample tube with the width d of 1cm, and stretching at the speed of 105mm min -1 The thickness h, initial length l, of the sample is recorded 1 And a subsequent length l 2 And the change of the tensile force F with time was recorded, and the tensile strength TS and the elongation at break E were calculated as follows b ：
TS(MPa)＝F/(2×d×h)
E b (％)＝(l 2 –l 1 )/l 1
Tests have shown that tubular films, E, prepared in a literature adhesive "face-to-face" bonding manner b 220% TS 4.4MPa, whereas the inventive water "face-to-back" laminate produced an ultralong tubular film, E b The TS is 306%, the TS can reach 16.8MPa, and the tensile strength is four times of a reported value in a literature, which proves that the invention greatly improves the compression resistance of the tubular membrane and prevents the phenomenon of liquid leakage in the tube.
Example 2: preparation of 3.2m long PVA tubular Membrane by Water bonding alkaline lye was separated in a 3D printing dialysis cell
The tubular film of this example was prepared similarly to example 1, except that 1000mL of PVA solution was coated on a glass plate in steps (2) and (3), and after free-running in a ventilated atmosphere, peeled off, and cut into 4 rectangular strips of 80X 7cm in size and 3 rectangular short strips of 7X 4cm in size. A80X 7cm rectangular strip is made into a single tube with the length of 80cm by a water bonding method, and then the single tubes are connected together by a 7X 4cm rectangular short strip, and after heat treatment, a tubular membrane with the length of 3.2m is formed.
The ultra-long tubular membrane obtained in this example was installed in a 3D printing dialysis tank and applied to semi-dynamic diffusion dialysis separation of NaOH/NaCl lye (1.69/1.79M), for comparison with example 1, the effective length of the tubular membrane immersed in the mother liquor was controlled to be 195cm, and the flow rate of the feed liquor was 178.8mL h -1 . The concentrations of the recovered liquid and the residual liquid were measured at 1 hour intervals, and the recovery rate and the retention rate were calculated, and the results are shown in the following table. The data show that the ultra-long tubular membrane has a certain separation effect on NaOH/NaCl feed liquid, but due to Cl - The ion volume is also smaller, the retention rate is obviously lower than that of Fe in the acid in the example 1 2+ Ion retention rate.
Results of separating NaOH/NaCl feed liquid from PVA tubular film prepared by water bonding method through 3D dialyzer are shown in the table
Example 3: preparation of PVA/TMOS ultra-long tubular membrane by hot water adhesion alkali lye separation in 3D printing dialysis tank
(1) Preparation of a coating liquid: the PVA solid is soaked in room temperature water for 10 hours, stirring is started, the temperature is raised from 50 ℃ to 92 ℃, the temperature is raised to 15 ℃ per hour, and finally the temperature is kept at 92 ℃ for 4 hours, so that the PVA solution with the mass concentration of 6wt% is obtained. Maintaining the temperature of the PVA solution at 65 ℃, dropwise adding TMOS into the PVA solution according to the mass ratio of Tetramethoxysilane (TMOS) PVA=0.3:1, namely dropwise adding 8.82mL TMOS into 500mL PVA solution within 0.5h, stirring at the same time, and continuing stirring at 65 ℃ for 24h after the dropwise adding is finished to obtain a coating liquid.
(2) Preparation of a single tube: uniformly coating the coating liquid obtained in the step (1) on a glass plate, and naturally drying in a ventilation environment to obtain a uniform flat sheet; after removal, 3 rectangular strips of size 7.5X75 cm and 2 rectangular short strips of size 8X 5cm were cut. The rectangular strip is rolled on a polytetrafluoroethylene tube with the outer diameter of 2cm to form a long tube shape, and the width of the overlapping area of the inner layer and the outer layer of the tube shape is 1.2cm. Applying 65 ℃ water to the outer layer surface of the overlapping area to wet the surface, wherein the water application amount is controlled to be 16cm per application area 2 1mL of water was consumed, and the two overlapping areas were bonded by pressing the outer layer against the inner layer to form a single tube 75cm in length. Repeating the steps to obtain three single tubes.
(3) Preparation of an ultralong tubular film: and (3) taking two single tubes obtained in the step (2), wherein one end of each single tube is sleeved on the same polytetrafluoroethylene tube, and the two ends are aligned and abutted. Completely wrapping two ends of two single tubes with a rectangular short strip with size of 8X15 cm to form inner layers at two ends and outer layers of the rectangular short strip, coating 65 deg.C water on the outer layers to wet the surfaces, and controlling the water amount at 16cm per coating area 2 1mL of water was consumed, and the two layers were bonded by pressing the outer rectangular short strips against the inner layer, so that the two single tubes were connected together by the rectangular short strips to form a tube 150cm in length. Repeating the steps, connecting a third single tube again to form an ultra-long tube with the length of 225cm, placing the ultra-long tube in an oven, heating from 60 ℃ to 130 ℃ per hour, and preserving heat at 130 ℃ for 4 hours to obtain the PVA+TMOS ultra-long tube type membrane.
(4) Static diffusion dialysis of ultralong tubular membranes in a 3D print dialysis cell: pva+tmos ultralong tubular membranes were installed in a 3D printing dialysis cell designed as in example 1. Static diffusion dialysis was performed on three stock solutions at low temperature (10 ℃) and the change in solution concentration was titrated, and the dialysis coefficient and separation factor were calculated from the membrane area, dialysis time and volume, calculated method reference (Journal ofApplied Polymer Science,37,2017,1-11).
The ultra-long tubular film was tested for performance, and the results showed that the ultra-long tubular film in this example had a water content of 73.7% and was soluble in water at 65℃for 8 daysThe expansion degree is 161.6%, the loss rate is 15.0%, and the material is soaked in 0.8MH at 65 DEG C 2 SO 4 The swelling degree after 2 days in the solution was 219.9%. Static diffusion dialysis showed that when the feed liquid was 0.8MH 2 SO 4 In the case of ethanol aqueous solution (volume ratio of ethanol to water is 1:1), H + Ion dialysis coefficient of 0.000446m h -1 . When the feed liquid is H 2 SO 4 /FeSO 4 Time (0.8/0.25M), H + Ion dialysis coefficient of 0.0011m h -1 The separation factor was 15.7. When the feed liquid is NaOH/NaCl (1.3/0.5M), OH - Ion dialysis coefficient of 0.00095m h -1 The separation factor was 2.4.
Example 4: preparation of PVA/PPO ultra-long tubular membrane by water bonding and separation of acid liquor in 3D printing dialysis tank
(1) Preparation of a coating liquid: preparation of 5wt% PVA solution As in example 1, an aminated polyphenylene ether hybridization solution (BPPO (+)/SiO) 2 ) The preparation method is the same as that of example 1 in Chinese patent ZL 201210206572.6. Filling 15g of ammonium polyphenyl ether hybridization solution containing solute into a constant pressure dropping funnel, dropping the solution into 900mL of PVA solution at 65 ℃ for 1.5h, and continuously stirring the solution for 24h at 65 ℃ after the dropping is finished to obtain coating solution;
(2) Preparation of single tube and ultralong tube membranes: the method is the same as in example 1, but the water temperature is selected to be 30-35 ℃ (the water temperature fluctuates) during bonding, and finally the PVA/PPO ultra-long tubular membrane (2 m) is prepared, the ultra-long tubular membrane is stored in water, and two ends are connected with plastic pipes.
(3) Semi-dynamic diffusion dialysis of ultralong tubular membranes in a 3D print dialysis cell: the design of the 3D printing dialysis cell was the same as in example 1, PVA/PPO ultra-long tubular membrane was wound and suspended outside the porous cylinder, which was then mounted at the bottom of the dialysis cell. Will H 2 SO 4 /FeSO 4 The acid liquor is introduced into the tubular membrane, the mother liquor is initially 4L of water, the liquid (residual liquid) flowing out of the ultra-long tubular membrane is collected every 1h, and the mother liquor is sampled, namely the recovery liquid.
When the flow rate of the acid liquid in the tube is 96mL h -1 At the time of 4 hours, H in the residual liquid flowing out of the tube + The ion concentration is reduced to 1.0M, H + Ion recovery was 79.7%, fe 2+ The ion retention rate is 78.1%; when the acid liquid in the pipe flowsThe speed is 150mL h -1 At the time of 4 hours, H in the residual liquid flowing out of the tube + The ion concentration is reduced to 1.20M, H + The ion recovery rate was 50.6% and the rejection rate was 88.6%. Indicating that with increasing flow rate, the recovery of acid decreases, while Fe 2+ The ion retention rate increases.
Finally, it should be noted that: the foregoing is merely a preferred example of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for preparing an ultra-long tubular film by water bonding, comprising the steps of:
s1, dissolving polyvinyl alcohol in water to form a polyvinyl alcohol solution with the mass concentration of 5-7%, wherein the polyvinyl alcohol solution can be directly used as coating liquid, or the temperature of the polyvinyl alcohol solution is kept at 50-70 ℃, the component A is dropwise added into the polyvinyl alcohol solution according to the mass ratio of the component A to the polyvinyl alcohol of 0.05-0.5:1, after the dropwise addition is completed for 0.5-1.5 hours, the heat preservation and stirring are continued for 6-24 hours, so that the coating liquid is obtained, and the preparation of the coating liquid is completed;
s2, uniformly coating the coating liquid obtained in the step S1 on a glass plate, drying in a ventilation environment to obtain a uniform flat sheet, cutting the obtained flat sheet into rectangular strips with long and short dimensions, rolling the rectangular strips with long dimensions on a polytetrafluoroethylene tube to form a long tube shape, wherein the width of an overlapping area of a long tubular inner layer and an outer layer is 1-1.5 cm, coating water on the surface of the outer layer of the overlapping area to wet the surface of the overlapping area, bonding the two layers of overlapping areas by pressing the outer layer to form a single tube, and repeatedly preparing a plurality of single tubes;
s3, taking the two single tubes obtained in the step S2, wherein one end of each single tube is sleeved on the same polytetrafluoroethylene tube, so that the two ends are aligned and close; completely wrapping two ends of the rectangular strip with short dimensions to form an inner layer at the two ends and an outer layer of the rectangular strip, coating water on the outer layer to moisten the surfaces of the rectangular strip, bonding the two layers by pressing the rectangular strip to attach the inner layer, and connecting the two single tubes together through the rectangular strip to form a longer tube; repeating the steps, connecting a plurality of single pipes to form an ultra-long pipe, performing heat treatment on the ultra-long pipe, and preserving heat for 2-6 hours at 120-130 ℃ to obtain an ultra-long pipe type membrane;
the component A is tetramethoxysilane, tetraethoxysilane, aminopropyl triethoxysilane, ammonium polyphenyl ether hybridization solution, hydrogen sulfonated polyphenyl ether hybridization solution or polysilicone copolymer.
2. The method for producing an ultralong tubular film by water bonding, as recited in claim 1, wherein: the length of the long rectangular strip in the step S2 is 30-90 cm, and the width is 5-9 cm; the length of the short rectangular strip is 5.5-9.5 cm, and the width is 3-5 cm.
3. The method for producing an ultralong tubular film by water bonding, as recited in claim 1, wherein: the amount of the water applied in the steps S2 and S3 is controlled to be 15-25 cm per coating area 2 1mL of water is consumed, and the temperature of the water is controlled between 15 and 65 ℃.
4. The method for producing an ultralong tubular film by water bonding, as recited in claim 1, wherein: in the step S3, the super-long pipes comprise 3 to 8 single pipes which are connected with each other.
5. An ultralong tubular film produced based on the production method of any one of claims 1 to 4.
6. Use of the ultralong tubular film of claim 5 in a 3D printing dialysis cell, wherein: the size and the model of the dialysis pond are designed through Rhino 7 and Shapr3D software, the 3D printing dialysis pond comprises a cuboid dialysis pond body and four hollow porous cylinders, the dialysis pond body comprises an inlet and an outlet, the bottom of the dialysis pond body is movably provided with the porous cylinders, and a plurality of the porous cylinders fix the ultra-long tubular membrane in the dialysis pond for diffusion dialysis separation of acid-containing or alkali-containing feed liquid.
7. Use of an ultralong tubular film in a 3D printing dialysis cell, as recited in claim 6, wherein: the dialysis tank body has a volume of 4-10L, and the porous cylinder has a diameter of 4-8 cm and a height of 10-18 cm.
8. Use of an ultralong tubular film in a 3D printing dialysis cell, as recited in claim 6, wherein: the method for fixing the ultra-long tubular membrane in the dialysis tank comprises the steps of coiling and hanging the ultra-long tubular membrane outside the porous cylinder, installing the porous cylinder at the bottom of the dialysis tank, introducing feed liquid or water into the tubular membrane, introducing corresponding water or feed liquid into the dialysis tank through an inlet as mother liquor, immersing the ultra-long tubular membrane in the mother liquor, and collecting the liquid and the mother liquor in the ultra-long tubular membrane after treatment is completed to obtain residual liquid and recovery liquid.
9. Use of an ultralong tubular film in a 3D printing dialysis cell, as recited in claim 6, wherein: the diffusion dialysis comprises static, semi-dynamic or dynamic;
when static diffusion dialysis is adopted, liquid is not input and output from two ports of the ultra-long tubular membrane, and neither the liquid in the tube nor mother liquid in the dialysis cell flows;
when semi-dynamic diffusion dialysis is adopted, one port of the ultra-long tubular membrane is used for inputting liquid, the other port is used for outputting liquid, and mother liquor in the dialysis tank does not flow;
when dynamic diffusion dialysis is adopted, one port of the ultra-long tubular membrane is used for inputting liquid, and the other port is used for outputting liquid;
mother liquor in the dialysis cell flows in from the inlet and flows out from the outlet.
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| CN102600730A (en) * | 2012-03-20 | 2012-07-25 | 北京坎普尔环保技术有限公司 | Preparation method for external pressure tubular membrane |
| CN104998551A (en) * | 2015-06-20 | 2015-10-28 | 杭州汉膜新材料科技有限公司 | Preparation method for internal-pressure tubular membrane |
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| CN110465204A (en) * | 2019-09-05 | 2019-11-19 | 盐城师范学院 | A kind of tubular membrane based on polyvinyl alcohol and preparation method thereof and the application in diffusion dialysis |
| CN114159983A (en) * | 2021-11-18 | 2022-03-11 | 中国科学院上海高等研究院 | Backwashing-resistant organic tubular membrane and preparation method thereof |
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| WO2012148068A1 (en) * | 2011-04-26 | 2012-11-01 | 제일모직 주식회사 | Hollow fiber membrane having a reinforced monofilament |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102600730A (en) * | 2012-03-20 | 2012-07-25 | 北京坎普尔环保技术有限公司 | Preparation method for external pressure tubular membrane |
| CN104998551A (en) * | 2015-06-20 | 2015-10-28 | 杭州汉膜新材料科技有限公司 | Preparation method for internal-pressure tubular membrane |
| US20190291054A1 (en) * | 2018-03-26 | 2019-09-26 | Xergy Inc. | Composite ion conducting membrane tubing and process of making same |
| CN110465204A (en) * | 2019-09-05 | 2019-11-19 | 盐城师范学院 | A kind of tubular membrane based on polyvinyl alcohol and preparation method thereof and the application in diffusion dialysis |
| CN114159983A (en) * | 2021-11-18 | 2022-03-11 | 中国科学院上海高等研究院 | Backwashing-resistant organic tubular membrane and preparation method thereof |
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